反应详情

温度

0 °C

To a suspension of NaH (60% dispersion, 1.14 g, 28.4 mmol) in dry THF (50 mL) under N2 was added CH3CN followed by 2-bromo-benzoic acid methyl ester (2 mL, 14.2 mmol). The reaction mixture was refluxed for 1.5 hour, then cooled to 0° C., quenched with water (1 mL), and concentrated in vacuo. The residue was diluted with water and the aqueous layer was extracted with hexane (2×), then acidified to pH 3-4 with 1N aqueous HCl. The milky aqueous layer was extracted with CHCl3 (3×), the combined organic layers were dried over sodium sulfate, filtered, and concentrated. Purification on silica gel with 0-35% EtOAc in hexane as eluent provided 1.89 g (59 % yield) of 3-(2-bromo-phenyl)-3-oxo-propionitrile as a yellow oil. 1H-NMR (d6-DMSO) δ: 11.8 (broad m, 1H, tautomers), 7.73 (broad s, 1H), 7.42 (m, 3H), 4.99 (s, 0.3H, tautomer), 4.64 (s, 0.6H, tautomer); HPLC/MS m/z: 223.9, 225.9 [MH]+.

1. temperatureThe reaction mixture was refluxed for 1.5 hour
2. customquenched with water (1 mL)
3. concentrationconcentrated in vacuo
4. additionThe residue was diluted with water
5. extractionthe aqueous layer was extracted with hexane (2×)
6. extractionThe milky aqueous layer was extracted with CHCl3 (3×)
7. dry with materialthe combined organic layers were dried over sodium sulfate
8. filtrationfiltered
9. concentrationconcentrated
10. customPurification on silica gel with 0-35% EtOAc in hexane as eluent